System for treating petroleum and petrochemical slop oil and sludge wastes

ABSTRACT

An initial chemical composition comprising selected surfactants, dispersants, and degreasers that liquefy, disperse, demulsify, degrease, inhibit corrosion and scale formation, and lower the pour point of a petroleum, coal, Fischer-Tropsch synthesized, or naturally occurring paraffin-based wax and asphaltene. Such a product is capable of converting crystalline wax (paraffin) in, for example, slop oil into an amorphous form of wax at room temperature, allowing the wax to be dissolved in, for example, crude oil without the need for heating, and maintaining it in solution at room temperature, substantially reducing, indeed in some applications, preventing, for example, wax build-up in pipelines, processing and transportation equipment, etc., and the recovery of the hydrocarbons in the slop oil. In a second aspect of the invention, the pre-blend addition of a hydrotrope-demulsifier, a chelating agent and a wax plasticizer can result in a BS&amp;W of zero for the recovered hydrocarbon blend.

REFERENCE TO RELATED APPLICATION/PATENT

This application is a continuation-in-part of Ser. No. 09/317,669 filedMay 24, 1999, which is being issued as U.S. Pat. No. 6,322,621 on Nov.27, 2001, the disclosure of which is incorporated herein by reference.

BACKGROUND

1. Field of Invention

The present invention relates generally to converting crystalline wax,as, for example, exists in slop oil, to an amorphous form of wax,causing it to be dissolvable in, for example, crude oil at, for example,ambient temperature and maintained in a dissolved state for a prolongedperiod of time at ambient temperature, and more particularly, in itspreferred, exemplary embodiment, to the use preferably of a chemicalcomposition of surfactants, polymeric dispersants and corrosion & scaleformation inhibitors that can, for example, recover waste hydrocarbonproducts (paraffin waxes, asphaltenes, and coke) from bothnaturally-occurring and synthetic sources, and more particularly torecover these waste hydrocarbon products for use as energy sources andto reduce environmental pollution. A number of other applications isalso disclosed and claimed.

Also, since the advent of new environmental laws for the disposal ofhydrocarbon based sludge, the petrochemical industries have implementedthe use of various types of cleanup systems. The most commonly usedmethods have been mechanical systems such as centrifuges, decanters,tricanters and various types and designs of liquid-solid separators.Most mechanical separation systems are limited by temperature and volumeconstraints.

Using mechanical systems alone, solid-liquid separations are nevercomplete. In order to obtain a complete separation with a minimum ofresidual emulsion rag (BS&W) remaining, chemicals are added to enhancethe efficiency of the separation. Since refinery and petrochemicalsludge oil residues are listed by the E.P.A. as toxic and hazardouswastes, they must be disposed of at a regulated special waste dump.Because of the limited amount of sites available for disposing suchtoxic and hazardous wastes, the disposal costs are extremely high.

In the year 2000 the average worldwide cost for disposal of these wastesranged from 350 to 500 dollars/metric ton (52 to 75 dollars per barrel)of sludge oil waste. Oilfield production slop oil and sludge wastes arealso a problem and are normally treated with the same methods used byrefineries.

2. Prior Art

For general background, “prior art” information pertinent to theinvention, reference is had to:

The Chemistry and Technology of Waxes by Albin H. Warth, published byReinhold Publishing Corp. (New York, 1947), p. 239 et al;

Petroleum Refinery Engineering by W. L. Nelson, published by McGraw-HillBook Co. (New York, 4th Ed., 1958), particularly Chapter 12 “De Waxing”(pp. 374-75 et seq.);

Physical Chemistry by Walter J. Moore, published by Prentice-Hall, Inc.(New York, 1955), particularly Chapter 16 “Surface Chemistry” (p. 498 etseq.); and

chemical and process technology encyclopedia edited by Douglas M.Considine, published by McGraw-Hill Co. (New York, 1974), particularlyits sub-section on “Waxes” (p. 1167 et seq.).

Also some patents cited in the parent application hereof include thefollowing—

Patent No. Inventor(s) Date 409296162 [Abstract Only] November 19976,000,412 Chan et al December 1999 5,525,201 Diaz-arauzo et al June 19964,551,239 Merchant et al November 1985 4,477,337 Rouden et al October1984

Also, the publications entitled “Cleaning Up the Slop: Part II” inHydrocarbon Engineering (December 1999) and the preceding article“Cleaning Up the Slop” (July/August 1999) are noted, but are notconsidered “prior art” in view of the priority date of the parentapplication (U.S. Pat. No. 6,322,621) for claims which incorporateinnovative aspects of the parent's technology, which are patentableeither alone or in combination with the new technology of the further,second aspect of the present invention.

Waxy materials present in crude oils and in the high boiling fractionsare considered to be crystalline throughout but under certain conditionsmay behave like a colloid. Certain wax solutions of refined productssuch as petrolatum, when agitated or mixed for long periods near or atthe crystallizing temperature, will form a completely transparent jelly.But the same solution, when chilled rapidly with moderate agitation willprecipitate a wax that can be centrifuged.

It was observed many years ago in the sweating of solid paraffins at thepetroleum refinery that three crystalline forms (manifestations) ofhydrocarbons are involved. These are known as “plate”, “malcrystal”, and“needle” [note, for example, The Chemistry and Technology of Waxes byAlbin H. Warth, published by Reinhold publishing Corp. (New York, 1947),p. 239]. It was recognized that the relative proportion of these typesof crystals not only has a relationship to the source of the crude butalso to the process of handling the wax.

The members of each series crystallize similarly as either plates,malcrystals, or needles. If one type is present (plate, mal, or needle),the crystal form remains the same regardless of such factors as theamount and kind of solvent.

When crude oil is pumped from the ground and transported throughpipelines, transported by ocean tankers, or stored in storage tanks onland or offshore, a large amount of heavy material separates and comesout of solution. The main component of this residue is high molecularweight paraffin waxes. In some cases the wax represents as much asninety (90%) percent of the deposited residues.

The amounts of wax present in crude oil are to a large extent anindicator of its origin, whether the crude originated in Venezuela,Mexico, or Malaysia.

This mixture of wax, oil, sand, and water is referred to as “slop oil,”or “slop,” in the petroleum industry. The percentage of slop oil variesaccording to the type of crude and the conditions under which it hasbeen transported. Usually the amount of slop oil ranges from a low of ahalf percent (0.5%) to a high of ten percent (10%); normally, it is inthe range of two percent (2% to 5%) to five percent.

For the last century and until today the only way to keep slop oil fromseparating from crude oil is to heat the slop oil while it is beingtransferred into mixing tanks with crude oil. The cost of keeping slopoil mixed with crude oil is a function of many variables such astemperature, solvent diluents, and residence time of the crude in a tankor pipeline.

The petroleum industry is plagued with the problem of having to delivercrude oil to refineries in a timely and economic manner. If a pipelinebecomes plugged up or clogged because of paraffin wax precipitating outduring the pumping operation, a crisis can arise. Numerous pipelinesworldwide are clogged daily or monthly due to wax precipitating out ofthe crude oil. Daily, 50,000,000 barrels of crude oil are pumped fromthe ground worldwide (as of May, 1999). If 5% of the heavy residues comeout of the crude oil being transported, whether by pipeline or tanker,the amount of slop oil or crude residue is 2,500,000 barrels per day.This amounts to 912,000,000 barrels per year. If 70% of this slop oil isuseable crude which can be processed to refine production, then theamount of recoverable hydrocarbon equals over 640,000,000 barrels peryear. At a cost of $10.00/barrel of crude oil this amounts to therecovery of $6.4 billion per year of useable hydrocarbon as eitherenergy or petrochemical feedstock.

Another important factor in the transportation of crude oil is thecorrosion of pipelines, storage tanks, and marine tankers. One of themain sites of corrosion in pipelines and storage tanks is at the pointof buildup of the paraffin wax. At this site corrosion-causing chemicalsbecome embedded in the wax and migrate to the metal surfaces. Pipelineswith intrinsically large wax buildup or settling have many morecorrosion problems than pipelines where the oil moves swiftly withoutdeposition occurring. This results in increased maintenance cost and insome cases pipelines have to be shut down and crude must be rerouted tonew lines as a result of both the clogged lines and corrosion. One ofthe main maintenance tools used to unclog crude oil pipelines is piggingthe line. In this process a small device shaped like a pig with a seriesof scrapers on its sides is shot through the line to remove all the wax.This wax is then collected at traps located along the line and shippedto pipeline pumping stations for storage.

In storage tanks the problems associated with wax settling out aretremendous and present an extremely challenging task to refiners andterminal operators.

When crude oil remains idle and cold in a storage tank, a heavy residueforms that, over time, accumulates at the bottom of the tank and reducesuseable tank volume. This residue, known as slop oil (or, slop),consists of heavy paraffinic waxes and asphaltenes which solidify incrystalline form. Slop oil is extremely difficult to remove from tanksand presents a very costly disposal problem for the refinery andterminal operator.

Traditional tank cleaning methods use a combination of heat (e.g., 60 to75 degrees C. or greater) and mechanical agitation to force the slop oilback into solution with crude oil, so the mixture can be pumped out ofthe tank. In order to keep the waxes and asphaltenes in solution withthe crude oil, the mixture must be kept at, for example, 75 degrees C.or greater and, in most cases, continuously circulated. The tremendousamounts of energy required to heat and circulate large volumes of densecrude oil to these elevated temperatures over long periods of timeincrease handling costs dramatically.

After pumping out the slop oil containing paraffin waxes andasphaltenes, the slop oil mixture must be kept hot or the wax willseparate from solution, and the problems associated with slop oil willrecur.

This need to use heat results in great energy cost and losses.

Also, as noted above, since the advent of new environmental laws for thedisposal of hydrocarbon based sludge, the petrochemical industries haveimplemented the use of various types of cleanup systems. The mostcommonly used methods have been mechanical systems such as centrifuges,decanters, tricanters and various types and designs of liquid-solidseparators. Most mechanical separation systems are limited bytemperature and volume constraints.

Using mechanical systems alone, solid-liquid separations are nevercomplete. In order to obtain a complete separation with a minimum ofresidual emulsion rag (BS&W) remaining, chemicals are added to enhancethe efficiency of the separation. Since refinery and petrochemicalsludge oil residues are listed by the E.P.A. as toxic and hazardouswastes, they must be disposed of at a regulated special waste dump.Because of the limited amount of sites available for disposing suchtoxic and hazardous wastes, the disposal costs are extremely high.

In the year 2000 the average worldwide cost for disposal of these wastesranged from 350 to 500 dollars/metric ton (52 to 75 dollars per barrel)of sludge oil waste. Oilfield production slop oil and sludge wastes arealso a problem and are normally treated with the same methods used byrefineries.

OBJECTS AND ADVANTAGES

The preferred, exemplary chemical compound mixture described herein willperform, inter alia, the following functions:

1. Converts the wax in, for example, the slop oil from a crystalline toan amorphous material;

2. Disperses the amorphous material into a diluent solvent;

3. Acts as a demulsifier which separates any water present in the slopoil;

4. Acts as a degreaser and works at a very low activity, e.g., 0.025%;and

5. Acts as a pour point depressant.

Since it acts as a wax liquefier and converts the wax to a lesscrystalline and more amorphous form, the slop oil waxes are readilydispersible into the crude oil medium. Thus a colloid is formedconsisting of heavy paraffin wax and asphaltene compounds dispersed incrude oil. Since the preferred, exemplary composition of matterdescribed herein also acts as a demulsifier, all water present in theslop oil mixture separates out, as well as the sand or grit present. Theheavy paraffin wax and asphaltenes are dispersed as hydrocarbon into thecrude oil and can be, for example, transported to the refinery forprocessing or to a marine tanker or other transport for shipment, forexample, at ambient temperature.

The use of the preferred, exemplary composition of matter describedherein, when, for example, injected into crude oil pipelines at, forexample, the production source, is capable of keeping the heavy wax andasphaltenes dispersed in the crude oil. Having the wax and asphaltenesdispersed one hundred (100%) percent into the crude oil will accomplishat least the following:

1. Lower maintenance costs by reducing the need to use costly piggingoperations on pipelines, which requires at least a partial shut-down ofthe pipeline;

2. Lower maintenance costs by reducing the problems associated withcorrosion in pipelines; with both items “1” and “2a” reducing the numberof downtime stoppages in the pipeline; and

3. Increase the throughput and flow rate of crude oil through pipelines.

The main goal and objective of a crude oil pipeline company is, forexample, to deliver to their customers a fixed amount of crude on anagreed-to, set schedule; every day that schedule is not met because oftechnical problems, the company loses money.

If the preferred, exemplary composition of matter described herein ismixed with crude oil loaded on, for example, marine tankers, theproblems associated with wax deposits will be at least greatlyinhibited, if not prevented from occurring, namely, slop oil residueswill be greatly reduced and indeed prevented from forming. In, forexample, oceangoing marine tankers the problems are twofold. At the endof many journeys the tankers have to go into drydock for maintenance dueto corrosion caused by slop oil settling out and coating the walls ofthe tanks.

The benefits of the preferred, exemplary chemical composition describedherein can be realized in, for example, the following ways:

1. Recovery of at least 640,000,000 barrels per year of hydrocarbons(based on a daily production of 50,000,000 barrels), which results in ayearly recovery value of approximately $6.4 billion at a world crude oilprice of $10.00/barrel. At a world crude oil price of $20.00/barrel theyearly recovery value would be $12.8 billion;

2. The projected cost for use of the composition of matter describedherein as a wax and asphaltene dispersant, liquefying agent, anddemulsifier would range in price at 1999 costs from a low of about$0.05/barrel to a high of about $0.42/barrel, depending on the injectionrate; and

3. The overall maintenance costs associated with pipeline transport,marine tanker transport, and storage tank cleaning could be as much as$0.10/barrel of crude oil produced or $2.0 billion per year.

In addition to the exemplary application of use with crude oil, thereare many other applications of the principles and teachings of thepresent invention, as detailed and exemplified below, all with greatutilitarian benefits.

Thus, some of the objects include the following.

It is thus an object of the invention to convert crystalline wax to anamorphous form by, for example, reducing its surface tension.

It is a further an object of the invention to convert crystalline wax toan amorphous form suitable for being dissolved in a desired or availablediluent, for example, in crude oil or other hydrocarbon, when dealingwith, for example, slop oil for, for example, recovery of thehydrocarbons in the slop oil and for enhanced transportation andpipeline movement of crude oil.

It is a still further object of the invention to provide a particularlyefficacious dispersant for wax or paraffin, while also preferablyproviding corrosion and scale formation inhibition, demulsifying anddegreasing, with preferably a homogeneous mixture.

It is a still further an object of the invention to provide enhancedcleaning of objects having, for example, a build-up of wax-containingsubstance(s).

It is a still further an object of the invention to provide cloud pointlowering of, for example, lube oil and the like, i.e., dehazing.

It is a still further an object of the invention to provide pour pointlowering of, for example, lube oil and the like.

It is a still further an object of the invention to provide a product orcomposition of matter and associated method for convertingcrystalline-wax-containing substances to an amorphous form in one ormore of the applications detailed below.

For a further understanding of the nature and objects of the presentinvention, reference should be had to the foregoing and the followinggeneral discussion and detailed description.

GENERAL DISCUSSION OF INVENTION First Aspect of Invention

The invention described herein in a very important, first aspect relatesto the use of a composition of matter or chemical composition and anassociated mixture that acts as, for example, a paraffin and asphalteneliquefying and dispersing agent and as a dispersing agent for coke andcoal fines. The dispersing medium can be, for example, a petroleum-basedproduct (such as crude oil or any refined petroleum product), aFischer-Tropsch-based product (such as liquid hydrocarbon productsderived from natural gas and byproducts of natural gas), coal, town gas,waste gases derived from animal and vegetable wastes, oils and organicsolvents derived from agricultural sources (such as, for example, edibleoils, furfural, alcohols, and other organic liquids) and water.

The source of the paraffin being liquefied and dispersed can be from,for example, petroleum, petrochemical, Fischer-Tropsch synthesis(including natural gas, natural gas liquids, coal, coal byproducts—peat,etc.), agricultural sources (carnauba-palm leaves, etc.), and animalsources (e.g., beeswax). The source of the asphaltene being liquefiedand dispersed can be, for example, from petroleum, petrochemical,Fischer-Tropsch synthesis, coal, and shale.

In accordance with this aspect of the invention a method for liquefyingand dispersing paraffin waxes and asphaltene containing, for example,petroleum products, can be dispersed into, for example, crude oil,refined petroleum products (such as diesel, fuel oil, etc.) and othersolvents such as water at room temperature. The dispersions remainstable at ambient temperatures over a long period of time. The preferredprocess of carrying out this invention includes, for example, the simplemixing of waste paraffin waxes and asphaltenes in the presence of crudeoil or any refined petroleum product mixed with the product describedherein at a concentration ranging from about 50 to about 100,000 ppm, ateither, for example, ambient temperature or at an increased temperature,e.g., the melt temperature of the paraffin wax, if so desired, with theoptimum concentration ranging from about 250 to 1,500 ppm.

The dispersion of the paraffin wax and asphaltenes tend to disperse moreeasily at higher temperatures using lower concentrations of chemicaldispersant. The ultimate result of mixing the wax and asphaltene withthe diluent is the same whether it is mixed at ambient temperatures(e.g., 21 degrees C.) or at higher temperatures (e.g., about 60 to about120 degrees C. or higher, if so desired), namely that the wax andasphaltene are dispersed in the diluent, whether, for example, crude oilor other refined products, and stays in solution for at least six (6)months, based on current tests, which are still on-going, if not longer.

Additional advantages of this preferred, exemplary application of theinvention, as well as other applications, will become apparent from thedescription which follows.

In other diluents, such as water, it was found that the wax in greasethat has oxidized for over, for example, three (3) years, can beinstantly liquefied and dispersed in water. The dispersion of the greasein water was passed through a water filtering system, with the endresult being water of a quality acceptable for reuse.

The principles and teachings of the present invention have broadapplicability, and a number of other, exemplary applications are listedbelow.

Second Aspect of Invention

Also, in a second aspect of the invention, a single step method ispresented whereby petroleum slop oil and sludge wastes from both oilproduction sites and refineries as well as petrochemical plants aretreated with a chemical composition that causes the sludge wastes toseparate into three distinct phases, solids (lower layer), water (middlelayer) and recovered oil (upper layer).

In the process presented as part of the second aspect of the invention,the sludge oil emulsion wastes also are treated with an organic aciddemulsifier described more fully below (in a range of about 0.015 toabout 7.5% by volume of waste treated) and a slop oil dispersant in therange of about 0.005 to about 2.5% by volume of waste treated) capableof liquefying any paraffins or asphaltenes present. The slop oildispersant described in U.S. Pat. No. 6,322,621 modified as per thesecond aspect of the invention preferably is capable of liquefying anyheavy hydrocarbons in the slop oil or sludge and dispersing thehydrocarbon present into diesel, light crude oil, heavy crude, asphalticcrude and/or crude oil tank bottoms.

All the solids present in the slop oil sludge emulsion are separated anddispersed into the water layer. Depending upon the amount of solidspresent the separation and settling times vary from 10 minutes to twodays. Solid compositions containing rust or iron oxides, silica (sand)and/or inorganic salts such as sulfates, carbonates and mixed salts ofalkaline earth metals and complex metal mixtures can be dispersed andwill settle out of solution completely. The water present separates as amiddle layer. Water clarity has been observed to be acceptable.

The process works in the following manner—to a reactor containing slopoil (sludge oil waste) is added, a slop oil dispersant described inApplicant's U.S. Pat. 6,322,621, as well as herein, modified, inaccordance with a second aspect of the invention, preferably in therange of 0.005 to 2.5% by value of waste treated). The concentration ofslop oil dispersant depends upon the type and quality of the slop oilsludge waste to be treated. To this mixture is added a water solutioncontaining an acid demulsifier (as described more fully below). Theamount of water added preferably should be not less than three times theamount of slop oil or sludge waste present.

The amount of acid demulsifier is 0.015 to 7.5%. This mixture is thenheated to 90 to 100° C. with stirring for at least 45 to 90 minutes orat least until a three-phase separation occurs. After a three-phaseseparation occurs, the temperature is lowered to 85° C. and a calculatedamount of hydrocarbon diluent is added to the mixture. The mixture ofslop oil, water, hydrocarbon diluent and chemicals (“505-SD-M”+“A-1000,”both more fully described and/or defined below) are heated and stirredfor an additional three hours at 80 to 90° C. The length of time neededfor stirring will depend upon the type of sludge oil being treated andthe hydrocarbon diluent used.

At the end of the prescribed time for heating at 80 to 90° C., the heatis removed, stirring is continued until the reactor reaches ambienttemperature. When the reactor reaches ambient temperature, stirring isdiscontinued. The contents in the reactor will separate into two mainlayers. The top layer will contain the recovered hydrocarbon from theslop oil being treated plus the added hydrocarbon diluent. The lowerlayer will contain water present in the slop oil being treated plus theadded water and the solids in the slop oil. On standing the dispersedsolids will separate resulting in a three-phase separation, top layer ofoil, middle layer of water and a lower layer of solids.

In this system the demulsifier breaks the slop oil emulsion of oil,water and solids. The slop oil dispersant disperses the solids presentinto the water and the hydrocarbon separating from the emulsion issimultaneously dispersed into the hydrocarbon diluent. These threephysical chemical processes are carried out simultaneously in thepresence of hot water and steam. Any paraffins or asphaltenes present inthe slop oil being treated are transformed to an amorphous state so theycan be dispersed into the hydrocarbon diluent present.

This synergistic process is aided by the presence of hot water andsteam, which act as a heat transfer medium. After the final separationoccurs the oil layer is pumped out to a storage tank. The recoveredwater can be transferred to another reactor for re-use in treatingadditional batches of slop oil sludge or back to a water treatmentplant, saving on the use of A-1000 (described more fully below). Thesolids are carted away for disposal. It has been found that therecovered water from the process yields a better separation when it isreused for future treatments.

The source of the water used in the process can be refining or processplant water, production wastewater, brine or any other type of availablewater. The best results have been obtained using the water recoveredfrom the primary slop oil treatment process.

Hydrocarbon diluents that have been used are diesel, Light Cycle Oil(L.C.O.), Vacuum Gas Oil (V.G.O.), Middle Distillate, Kerosene, crudeoil (light or heavy), crude oil tank bottoms, asphalt crude and fueloil. When refinery sludges are treated the best results are obtainedusing Light Cycle Oil, Middle Distillate, Vacuum Gas Oil, fuel oil andcrude oil. This is especially the case with refinery sludges containinghigh concentrations of paraffins and asphaltenes. When treating oilproduction sludges the best hydrocarbon diluents are the crude oil fromwhich the sludge originates. For example, asphalt waste sludges from anasphalt crude production site are best treated with the asphalt crudefrom which the sludge originated. The same would apply to heavy paraffinwax sludges. In practice we have found that in the case of heavy waxysludges the best diluent for dispersing the recovered waxy product isthe crude oil from which it originated.

DETAILED DESCRIPTION Exemplary Initial Chemical Composition (1^(st)Aspect)

The preferred, exemplary composition of matter or chemical compositionor exemplary, currently preferred, wax liquefier and dispersant of afirst aspect of the invention is a homogeneous mixture (preferably puresolution, one phase) of

about 25% to about 99.5% by weight of surface active agent,

about 15% to about 35% by weight butyl cellosolve,

about 5% to about 15% by weight of pine oil and a specially mixedcatalyst solution made of saturated higher fatty acids, an alkly phenoland an oil-water soluble copolymer of partially sulfonated, maleicanhydride and polystyrene with a molecular weight ranging from about2,000 to about 2,000,000. The catalyst mixture normally is present in arange of about 0.5% to 5%, with all percentages being “by weight”percentages.

One particularly preferred, exemplary composition is about 48% surfaceactive agent in the form of a nonionic polyethoxylated compound, e.g.,one derived from polyethylene oxide, which has a H.L.B. number of 11.0.

As is known in the surfactant art, an H.L.B. number represents afundamental property of a nonionic surfactant that correlates with bothphysical properties and surface active effects. The H.L.B. number is ameasure of the hydrophilic and lipophilic (hydrophobic) characteristicsof the surfactant molecule. In a series of surfactants prepared by theethoxylation of an alcohol or amine, for example, the ratio ofhydrophilic to lipophilic portions increases with the increasing degreeof ethoxylation. This corresponds to an increase in hydrophiliccharacter—or water solubility—of the molecule. The H.L.B. number of thesurfactant determines the type of emulsion produced as well as thestability of the emulsion. A water-in-oil (W/O) type of emulsionrequires emulsifiers of low H.L.B. number, e.g., about four (4) [100%water insoluble-non-dispersible in water)], while an oil-in-water (O/W)type requires emulsifiers with higher H.L.B. numbers, e.g., nine tosixteen (9-16). Surfactants with H.L.B. numbers near thirteen (13) aredetergents, and those of fifteen to sixteen (15-16) are stabilizers. Thesurface active agents in the currently preferred, exemplary productpreferably have a H.L.B. number ranging from about ten to about elevenand a half (10-11.5) and are considered to be good re-wetting agents(low contact angle) and are good emulsifying and dispersing agents foroils and solids.

Another factor to be considered is the addition of a surface tensiondepressant. In order to enhance the effectiveness of the surface activeagent, for example, a fluorocarbon alcohol is added to lower the surfacetension of the composition of matter. Normally the amount added is, forexample, 0.1%. Therefore, the surface active agent consists of anonionic surfactant that is made up of, for example, about 99.9% of apreferably commercially available, nonionic polyethoxylate surfactantand, for example, about 0.1% of a surface tension depressant in the formof, for example, a flouronated hydrocarbon alcohol. The range of surfacetension for the final composition of matter ranges from about 10 toabout 48 dynes/cm and more preferably from about 15 to about 32 dynesper cm.

The by-weight percent of the nonionic surface active agent is preferablyabout 48%, with about 32% butyl cellosolve and about 17% pine oil (withboth of these latter components acting as a degreaser), about 3% of amixture containing about 70% higher fatty acids, about 29% a copolymerof partially sulfonated, maelic anhydride and polystyrene, and about 1%of catechol (serving as a corrosion inhibitor).

The foregoing, preferred chemical mixture is referenced herein as“505-SD.”

Other surface active agents, which may be used in place of or incombination with the exemplary polyethylene-oxide-based, nonionicsurfactant, are outlined below.

-Types of Nonionic Surfactants- H.L.B.# 1. Ethonylated Alcohols tridecylalcohol ethoxylate (6 EO) 11.4 (where EO is ethlyene oxide) tridecylalcohol ethoxylate (9 EO) 13.3 tridecyl alcohol ethoxylate (12 EO) 14.5tridecyl alcohol ethoxylate (15 EO) 15.3 Witco Chemicals' tridecylalcohol ethoxylate 12.4 Stepan Chemicals' tridecyl alcohol ethoxylate12.4 alcohol ethoxylate (3 EO) 8.0 alcohol ethoxylate (6 EO) 11.8alcohol ethoxylate (8 EO) 13.2 alcohol ethoxylate (10 EO) 14.1 C₈-C₁₀alcohol ethoxylate (6 moles) 12.5 C₈-C₁₀ alcohol ethoxylate (8 moles)13.6 2. Reactions of Cocoacid + Polyethylene Glycol (PEG) PEG30 -glyceryl cocoate 15.9 PEG80 - glyceryl cocoate 18.0 PEG30 mixture -glyceryl cocoate 15.9 PEG20 - glyceryl tallowate 13.0 PEG80 - glyceryltallowate 18.0 PEG200 - glyceryl tallowate 19.0 PEG2 cocamine 6.2 PEG5cocamine 11.0 PEG10 cocamine 13.8 PEG15 cocamine 15.4 PEG15 cocaminemixture 15.4

It is noted that, as the amount of ethoxylation increases, the H.L.B. #increases, and the cationic character changes to more nonionic.

PEG2 tallow amine 5.1 PEG2 tallow amine mixture 5.1 PEG5 tallow amine9.2 PEG10 tallow amine 12.6 PEG15 tallow amine 14.4 PEG15 tallow aminemixture 14.4 PEG20 tallow amine 15.4 3. Other Commercially Available,Nonionic Surfactants Nonylphenol (5 EO) 6.8 Nonylphenol (10 EO) 11.0Nonylphenol (12 EO) 12.2 Nonylphenol (15 EO) 13.5 Nonylphenol (18 EO)19.5

3. Other Currently Non-Commercially Available, Nonionic Surfactants

a. nonionic surfactant formed from α-diol condensation products;

b. polyhydroxyl nonionic compounds;

c. nonionic surfactant formed by the reaction of an ethoxylated Schiffbase with a methyl alkyl ketone;

d.i-alkyl-polyethylene-polyamines reacted with maleric acidsemiamide—nonionic compound with antibiocide properties;

e. nonionic surfactant derived from polyethoxylated alcohols+vinyl-alkylethers;

f. biodegradable glycidol surfactant (nonionic), e.g., alcohol+glycidol(with catalyst) producing nonionic surfactant (biodegradable);

g. multiblock polyacetal copolymer surfactants, e.g., poly-propyleneoxide or poly-ethylene oxide+dialkyl ether;

h. urea-ethoxamer nonionic inclusion compounds, e.g.,urea+polyethoxylated long chain alcohols; and

i. polyglycol ethers+polyglycol₆₀₀₀+epichlorohydrine derived nonionicsurfacts; etc.

Exemplary Applications

Some exemplary applications of the principles and compositions of afirst aspect of the present invention are listed below:

1. Cleaning crude oil and petrochemical storage tanks;

2. Injection into crude oil pipelines to prevent wax or “slop”separation;

3. Add to crude oil in oceangoing vessels to prevent wax or “slop”separation;

4. As a dispersant in base lube oil stocks to lower the cloud point,namely as a dehazing compound;

5. As a wax liquefier and dispersant in base lube oil stocks to lowerthe pour point;

6. As a dispersant in gasoil to lower the cloud point, namely as adehazing compound;

7. As a wax liquefier and dispersant in gasoil to lower the pour point;

8. As a demulsifier for crude oil in pipelines and storage tanks;

9. As a wax liquefier in downhole operations in the production of crudeoil;

10. As a dispersant and degreaser in crude oil storage tanks;

11. As a dispersant and degreaser in petrochemical storage tanks;

12. As an additive in engine lubricating oil for the purpose ofdispersing lubricating oil sludge;

13. As a method of measuring the true value of crude oil by demulsifyingthe water in the crude oil; this will allow for a more accuratemeasurement of the actual amount of crude oil being purchased;

14. As a dispersant and wax liquefier in hydrocarbon liquids derivedfrom natural gas processing, i.e., condensates;

15. As a dispersant for napthenic acids in fuel oils;

16. As a dispersant for sludge in processing units such as catalyticcrackers;

17. As a dispersant for waste wax residue derived from polyethyleneplants for the purpose of dispersing the wax into fuel oil;

18. As a dispersant for wax in cutting and cooling fluids used inmachining operations;

19. As a dispersant for wax in heavy fuel oils such as, for example,“Bunker C” and Fuel Oil No. 6 (heating oil);

20. As a wax liquefier and degreaser in heat exchangers in variouspetroleum refining process units (e.g., furfural lube oil extractionplants);

21. As a dispersing agent for coke and carbon fines into hydrocarbonliquids and/or water;

22. As a dispersant for cleaning machine parts;

23. As a liquefier and dispersant for wax into hydrocarbon liquidsderived from Fischer-Tropsch synthesis;

24. As a dispersant for wax in edible oils;

25. As a dispersant for wax in organic solvents;

26. As a dispersant for asphalt in various hydrocarbon solvents;

27. As a dispersant in cutting oil emulsions;

28. As a dispersant for naturally-occurring waxes in various hydrocarbonmedia and water;

29. As a liquefier and dispersant for wax used as a protective coating;

30. As a dispersant and liquefier for wax for oil recycling processes;

31. As a dispersant for highly-paraffinic organic compounds into variousorganic solvents;

32. As a liquefier and dispersant additive in gasoline and fuel oil;

33. As a degreaser for removing asphalt from concrete surfaces;

34. As a neutral metal degreaser for metal parts in dip tanks;

35. As a liquefier for wax derived from pipeline pigging operations;

36. As a dispersant in oil for extreme pressure additives (E.P.A.);

37. As a dispersant in oil for anti-wear additives;

38. As a dispersant in lube oil to provide dispersion of products ofdegradation and combustion;

39. As a dispersant for fuel oil (e.g. “Bunker C”), diesel and gasoil;

40. As a dispersant for wax in solvent dewaxing processes;

41. As a dispersant for metals and sludge in petroleum waste products(e.g. oil/water separators);

42. As an additive for drilling muds to enhance their dispersion andsurface active activity (contact) during drilling operations;

43. As an additive in petroleum production to enhance the flow of crudein secondary and tertiary production;

44. As a wax liquefier and dispersant in the production of

a. floor coverings and polishes,

b. adhesives,

c. cosmetics,

d. electrical insulation,

e. leather finishes,

f. matches,

g. treated paper products,

h. molding and coating processes,

i. printing inks and varnishes,

j. dental materials,

k. explosives,

l. crayons,

m. textile finishes,

n. candles,

o. rubber antioxidants,

p. corrosion inhibitors, etc.;

45. As a surface active agent and dispersion in descaling formulations;

46. As a surface active agent and dispersion in acid de-rustingformulations;

47. As a wax liquefier and dispersant in high-heat distillates (e.g.lignitic tar-lignite paraffins);

48. As a dispersant for asphalt and/or tar on surface coating such as,for example, roofing paper;

49. As a cleaning chemical in the cleaning of ship ballast tanks;

50. As a wax liquefier and dispersant in emulsions used in automobileand other vehicular care products (i.e., transportation cleaners);

51. As a biodegradable dispersant for agricultural fertilizers for treesand plants;

52. As a wax liquefier and dispersant in the manufacture of grease;

53. As a dispersant for inorganic compounds in water, such as tailingsfrom mining;

54. As a dispersant and demulsifier for waste oil in oil production,exploration, transportation and refineries (A.P.I. separators); and

55. As a dispersant for wax in commercial car products to help in theself-rinsing applications; etc.

Exemplary Method for Recovering Slop Oil Tank Bottoms

At ambient temperature [e.g., 75° F. (degrees Fahrenheit), 24° C.(degrees Celsius)], slowly add 0.13 kg (0.286 lb.) of the exemplarycomposition to 10 kg (22 lb.) of slop oil under intense and vigorousmixing. Mix the two components throughly. After a homogeneous mixturehas been achieved, immediately add 30 kg (66 lb.) of crude oil to themixture of slop oil and the preferred composition. Continue mixing untila completely homogeneous mixture is obtained. This should take no longerthan fifteen (15) minutes using the amounts specified.

During the mixing process water and sand will be observed separatingfrom the mixture. The crude oil must be added with vigorous agitationeven if water is separating during mixing. After a completelyhomogeneous mixture is obtained, cease agitation and allow the mixtureto stand for three to four (3-4) hours.

After allowing the mixture to stand for three to four (3-4) hours, aseparation layer of water and sand will be observed on the bottom of thetank; the mixture of crude oil and the composition will remain on top.The viscosity of the new hydrocarbon fraction will be low and the layerwill be completely homogenous; there should be no lumps or pieces ofparaffin floating in the hydrocarbon fraction.

Separate the water/sand layer from the mixture by, for example, pumping.The crude oil mixture may then be transferred to a storage tank and onto further processing.

Tests of Initial Composition

A number of tests have been run showing the efficacy of the presentinvention, with the first six (6) tests using the preferred compositionor combination described above as preferred.

Test #1

The addition of a two (2%) percent dispersant to one (1) barrel of slopoil/tank bottoms under rapid mixing at 80 degrees C. (176° F.), followedby the addition of three (3) barrels of crude oil (at ambienttemperature) resulted in a crude oil blend that was stable (no waxprecipitates) for well over nine (9) months.

Test #2

A three (3%) percent dispersant was added to one (1) barrel of slopoil/tank bottoms at 40° C. (104° F.) under constant rapid mixing,followed by the addition of two (2) barrels of crude oil (at ambienttemperature). The resulting product was a homogeneous and viscous blendof crude oil and slop oil/tank bottoms that showed no separation of theslop oil/tank bottoms component from the blend. The blend continues toremain homogeneous and viscous at ambient temperature for a period sofar of well over nine (9) months.

Test #3

A small sample (50 grams) of heavy waxy slop oil was taken from an oldstorage tank; the slop oil had been in the tank for over ten (10) years.The slop oil was melted into a liquid mass at a temperature ofapproximately 80 degrees C. and stirred to obtain a homogeneous mixture.Two (2) ml of dispersant was added to the liquefied wax and theresulting blend was stirred for two (2) minutes at approximately 75° C.

After it was determined that the dispersant was thoroughly dispersedthroughout the liquefied wax, 150 ml of crude oil tank bottoms (anextremely viscous liquid oil fraction) was added to the mixture and theresultant blend was stirred for an additional ten (10) minutes at 75° C.to obtain a homogeneous mixture. The mixture was removed from the heatand allowed to cool down to ambient temperature (25 to 30° C.). Afterreaching ambient temperature the mixture was separated into two halvesand poured into glass bottles for observation. Each sample indicated twolayers—a clear, oil-free water layer on the bottom that containedsuspended solids (sand, etc.) and an upper layer of oil.

The samples were allowed to sit for a period of one hundred and twenty(120) days during which time it was observed that the oil layer remainedcompletely homogeneous. There was no separation of any solid waxmaterial. One of the samples was centrifuged at ambient temperature andthree (3) layers were formed: a layer of sand and grit (3%); a layer ofwater (27%); and a layer of oil (70%). The oil layer remainedhomogeneous for a period of over seven (7) months; there was noseparation of any solid paraffin. The oil layer remains homogeneous withno separation.

Test #4

To a reactor containing 10 kg of slop oil was added 30 kg of heavyArabian crude oil containing 0.5 kg of dispersant. The mixture wasagitated to a thoroughly homogeneous state for a period of one and ahalf (1½) hours. At the end of this period 38 kg of the crude+slophydrocarbon was pumped out. The resulting mixture remained homogeneousfor two (2) weeks; a layer of sand and water separated out of solution.The sand was pumped off and cleaned using the dispersant.

Test #5

In this test a steel machine gear heavily encrusted with hardened greaseand dirt was immersed in a solution of dispersant and water. This gearhad been stored outside, fully exposed to the elements, and had not beenhandled or moved for at least five (5) years. After being allowed tosoak in the solution for a short time, the grease and dirt softeneduntil only slight finger pressure would remove it. The solution wasagitated for a few minutes and the grease and dirt completely dispersedinto the solution. The gear was removed from the solution and thesolution was allowed to stand. The grease remained suspended in thedispersant solution.

Test #6

A 50 gm sample of wax residue from a polyethylene production plant washeated to 120° C. To this heated sample was added 0.5 gms of theinvention's exemplary composition of matter. The mixture was agitateduntil complete homogeneity was observed at 120° C. To the heated mixtureof polyethylene waste wax plus compound was added 200 gms of fuel oil(#6 fuel). The fuel oil was added to the mixture at 120° C. This mixturewas stirred until complete homogeneity was observed at 120° C. When ahomogeneous mixture was observed, the heat was taken away and themixture was allowed to cool down to room temperature. After the mixturereached room temperature, it was observed that no wax separated out ofsolution. After a period of two (2) months, still no separation of waxwas observed.

Test #7

To check for its dehazing or cloud point lowering capabilities, to asample of processed lube oil was added a modified mixture of theexemplary, usually preferred, composition of matter or product, namely,only the surface active agents (namely, polyalkylethoxylated alcoholplus nonylphenol plus a flourinated polyethoxylated alcohol) and adispersing agent polymer derived from a copolymer of partiallysulfonated, maleic anhydride and polystyrene, with the surface activeagent and the dispersing agent being present in a ratio of two hundredto one (200:1), namely 99.5% to 0.5% by weight, was used.

At a concentration of five (500) parts per million (ppm) the cloud pointof the lube oil was reduced from +15 degrees C. to +3 degrees C. Thistest was repeated at a concentration of two hundred and fifty (250) ppmand then of a thousand (1,000) ppm. The cloud point was reduced to +6°C. and +3° C., respectively. The results are summarized in the followingtable.

Reduced Cloud Point (degrees C.) Concentration (ppm) from +15° C.   2506   500 3 1,000 3

Test #8

A test was performed, whereby coke from a delayed coker unit at arefinery was treated with the preferred composition of matter in aheated water mix, and the following results were obtained:

Water plus a half (0.5%) percent by weight of the invention's preferredcomposition of matter were mixed together and heated to about 200° F.,with the coke in chunk form dropped into the stirred hot water andcomposition of matter mix. All of the coke treated was found to becompletely dispersed in the heated mixture. Such dispersal would nothave occurred without the presence of the added composition of matter ofthe invention.

The coke used in the test was from a stub tower and the blow-down towerfrom the delayed coker unit. The test showed that, with the coke beingin the dispersed state, the coke could be easily removed from the unitas a dispersion in water and thus easily removed from the site.

Exemplary Enhanced Chemical Composition or Mixture (2^(nd) Aspect)

In a second aspect of the invention, the following three (3) ingredientsare included with “505-SD” (defined above):

1. The addition of a plasticizer or leveling agent (a/k/a a de-airingagent) increases the conversion rate of crystalline wax (platelets,needles, microcrystalline and/or macrocrystalline) to the amphorous formof wax (mal). The typical plasticizers are phosphate esters, phthalateesters, adipate esters and/or benzoate esters.

The preferred esters are the following:

a. tributoxyethylphosphate (KP-140);

b. tributyl phosphate;

c. tri-isobutyl phosphate;

d. tris (2-ethylhexy) phosphate Flexol TOF (Reomol TOF);

e. tricresyl phosphate;

f. dioctylpthalate;

g. diethyl pthalate;

h. di-(2-ethylhexyl) adipate-Flexol-A-26;

i. di-(n-hexyl) phthalate-Flexol DHD;

j. di-(2-ethylhexyl) phthalate-Flexol DOD;

k. diethyleneglycol, dibenzoate-Flexol 2 GB;

l. triglycol di (2-ethylbutyrate)-Flexo 3 GH;

m. polyethylene, 200 di (2-ethyl hexoate)-Flexol 4GD;

n. triglycol di (2-ethylhexoate)-Flexol 3GO; and

o. di (2-ethylhexyl) tetratrihydrophtalate-Flexol-8HP.

When a plasticizer from the group listed above is mixed in a range ofconcentration by weight of about five-hundredths (0.05 to 65%) aboutsixty-five percent with the “505-SD” formulation, the liquefaction rateof wax is increased markedly.

2. When a hydrotrope-demulsifier and a chelating agent are mixed withthe afore described “505-SD” formulation mixture, the solubility of thewax increases substantially in a hydrocarbon solvent, with a separationof water and solids from a slop oil wax emulsion to form a three-phaseseparation (oil-wax, water and solids).

The recommended hydrotrope-demulsifiers are as follows:

a. Sodium Xylene Sulfonate;

b. Sodium Dodecyl Sulfonate;

c. Sodium Cumene Sulfonate;

d. Ammonium Cumene Sulfonate;

e. Sodium Napthalene Sulfonate; and

f. Sodium Napthenic Acid Sulfonate;

3. The preferred chelating agents are:

a. Ethylenediamine tetraacetic acid (Versene);

b. Sodium salt of Ethylenediamine tetraacetic acid;

c. Nitrilotriacetic acid (NTA); and

d. polymeric chelating agents derived from copolymers of acrylic andmaleic acids.

When a chelating agent from the group of those listed above is added ina range of about two to about twenty-five (2 to 25%) percent and one ofthe hydrotrope-demulsifier in the group listed above is added in therange of about five to about fifty (5 to 50%) percent to a mixturecomprising a plasticizer from the group listed above in a range of aboutfive hundredths (0.05 to 65%) to about sixty-five percent to theformulation afore-described as “505-SD.” The resulting mixture reachingone hundred (100%) percent of the above described components results ina product that will allow crystalline wax or low A.P.I. gravity asphaltresidue emulsion to become solubleized (dispersed) in a crude oildiluent with a complete separation of hydrocarbons, water and solids. Inother words, a three-phase separation.

An exemplary, preferred combination of the ingredients for “505-SD” andthe additional three ingredients of the foregoing, the combination ofwhich is referenced herein as “505-SD-M,” includes the following.

To a four (4) liter (4,000 ml) beaker equipped with a stirring mechanismis added at room temperature the following chemicals in the order listedbelow:

Part A:

1. Sodium Xylene Sulfonate (40% active)=1,200 ml (1,420 gms),

2. Dissolvine 39 (E.D.T.A. Sodium Salt (39% active)=120 ml (155 gms),

3. Butyl Cellosolve=250 ml (225 gms),

4. Mixture of Nonionic Surfactants=55 ml (53.4 gms), (AlcoholExthoxylate 9.5)

5. Mixture of Nonionic Surfactants=80 ml (84 gms), (NonyhexthoxylatedPhenols, 4-EO, 6-EO and 12-EO),

6. KP-140 (tributoxyethyl phosphate)=51.0 ml (52.0 grms),

7. “Zonyl FSN” (Nonionic fluorosurfactant; a fluorinated polyethoxylatedalcohol, 47% active)=6.0 ml (6.1 gms),

8. Butyl Cellosolve=1,053 ml (950 gms), and

9. Pine Oil=528 ml (502 gms).

To this mixture is slowly added a pre-blend of the followingingredients.

Part B:

1. Vegetable Oil=120 ml (108 gms),

2. Copolymer of maleic acid+polystyrene-sulfonated (25% active)=15 ml(17.9 gms), and

3. Mixture of o-cresol plus p-cresol=2.0 ml (1.9 gms).

The final mixture is prepared by adding slowly Part B to Part A at roomtemperature. Part B is an emulsion that clears up when added to Part A.The total volume is 3,450 ml.

The percentages by volume of each component to the final composition ofPart A+Part B are

Part A + Part B: Sodium Xylene Sulfonate (40% active) = 35.00%  E.D.T.A.(39%) = 3.50% Butyl Cellosolve = 7.00% Nonionic Surfactants = 4.00%KP-140 = 1.50% Zonyl FSN (Fluorosurfactant surface tension reducer) =0.10% Butyl Cellosolve = 31.00%  (total with above 38%) Pine Oil =15.00%  Vegetable Oil = 2.50% Polymer Dispersant(Maleic-Polystyrene-Sulfonate) = 0.50% O/P Cresol = 0.05% TOTAL =100.15% 

EXAMPLES Example #1 (Also See Summary Test Report Table Below)

Step 1: Two hundred (200) ml of oily emulsion sludge from T-101 (a tankcontaining wax emulsion rag stored by Salah-Sarawak Shell at the ShellE&P International Labuan Crude Oil Terminal in East Malaysia) was placedin a 400 ml glass beaker and heated to between 85-90° C. with mixing (amagnetic stirring bar was used as the method of mixing). To the twohundred (200) ml of sludge was added a half (0.5) ml of a formulationcomprising a mixture of a hydrotrope-demulsifier (45% by wt sodiumxylene sulfonate) a chelating agent (20% by wt. ethylenediaminetetra-acetic acid) a wax plasticizer (10% by wt. of tributoxyethylphosphate) and 25% by wt. the formulation mixture “505-SD” (0.25% byvolume) of sludge emulsion treated. The mixture of sludge emulsion anddispersant was heated and mixed continuously for a period of fifteen(15) minutes.

Step 2: Two hundred (200) ml of water was heated between abouteighty-five to about ninety (85 to 90° C.) degrees Centigrade withmixing (a magnetic stirring hot plate was used as the mixing and heatingmethod). When the temperatures of the water reached 85° C., two (2) mlof a mixture of 40% by wt. of water and 60% by wt., a weak organic acid(typical organic acids that can be used are citric acid, sulfamic acid,oxalic acid and/or glycollic acid; referenced herein as “A-1000;”1.00%by volume was added). The mixture was allowed to continue to mix for anadditional ten (10) minutes.

Step 3: After both mixtures had been heated and stirred for a periodoften (10) minutes at 80 to 85° C., the beaker containing the twohundred (200) ml of water and “A-1000” was added to the beakercontaining two hundred (200) ml of sludge emulsion and “505-SD.”Immediately upon addition of the water “A-1000” solution to the sludgeemulsion “505-SD” mixture, a separation occurred. The initial solutionseparated into three layers: a black upper layer of oil, a brownishmiddle layer of water, and a dark brown layer of solids dispersed inwater.

Step 4: After the three layers had cooled to 75° C., fifty (50) ml oflight crude oil (Shell L.C.O.T. export crude oil) was added to themixture (400 ml of treated materials in a blend of light crude, water,and demulsified sludge plus chemicals was heated up to 80° C. andstirred for an additional 10 minutes.) The total blend was allowed tocool to room temperature. At room temperature, two distinct layers wereformed: the upper layer of light crude plus recovered hydrocarbon and alower layer of water plus solids dispersed in the water. As thetemperature reached room temperature (25° C.), the solids began tosettle out of the water.

The separation level of water and oil was as follows:

Total oil recovered = 215 ml Less light crude added = −50 ml Net amountof oil recovered = 165 ml (Percentage of oil recovered = 82.5%)

In this example the ratio of light crude to recovered sludge crude isbout 0.3 to 1.0. In terms of barrels of light crude oil used to barrelsof crude oil recovered, the ratio is 0.3 bbls of light crude to 1.0 bblsof recovered emulsion crude.

Analysis of the Crude Oil Blend

A sample of the final crude oil blend was sent to the terminallaboratory for testing. The two tests of interest were the BS&W (ASTMD4007-81) and pour point (ASTM D97-96a). The following results wereobtained on the final crude oil blend:

Result “Acceptable limit” BS&W = 0.00% <2.00% Pour point = 10° C.) <15°C.) (The “acceptable limit” is the standard set by the terminal forexport grade crude oil.) The unprecedented achieving of a BS&W = 0.00%should be noted.

TANK 101 SLUDGE TREATMENT MONITORING REPORT Report Reference:TK101/014/99 Job Request Ref: Taken from: ESP Treatment Plant SampleDescription: K♦P.Crude Holdong TKS Taken by: Jahari Junaidi Indicator:EPT-DPC Date/Time: Feb. 11, 1999 @ 1000 Hrs Received By: Jahari JunaidiIndicator: EPT-DPC Date/Time: Feb. 11, 1999 @ 1000 Hrs TESTS UNIT RESULTMETHOD ACCEPTABLE LIMIT Treated Crude Bottom Sediment and Water (B S & W%) % Vol. See Below ASTM D 4007-81 <2.00% Density @15° C. Kg/l 0.8863ASTM D 1298-85 Pour Point ° C. 10.0 ASTM D 97-98a <15° C. Effluent Oiland Grease by Gravimdrie mg/l N/A APHA 5520 B <500 mg/l pH N/A<pH5-pH8.5 Comments: B.S. & W % 0.00 Emulsion % 1.40 OH % 98.60 Testresults shall not be reproduced, except in full, without writtenapproval from the Laboratory. The above results relate only to the itemstested. Analysed: Johari Junaidi Checked by: Indicator: EPT-DPCIndicator: Date Feb. 11, 1999 ten 1140 Hrs Date:

[Also see Article entitled “Cleaning Up the Slop: Part II” inHydrocarbon Engineering (December 1999) and the preceding article“Cleaning Up the Slop” (July/August 1999), the contents of which areincorporated by reference.]

Additional Case Studies

A series of tests were performed at Calumet Lubricants Refinery inPrinceton, La. The samples tested are from on site slop oil tanks withhigh concentrations of BS&W rag layers. The rag layers have a largeconcentration of water and paraffin. The solids content is relativelylow.

Lab Experiment #1:

Two hundred (200) ml of Tank 5067 (Calumet Lubricants, Princeton, La.)was mixed with one (1) ml of “505-SD-M” and heated to 86° C. (187° F.).Separately six hundred (600) ml of tap water was mixed with five (5) mlof “A1000” and heated to 86° C. (187° F.). The two heated componentswere mixed and stirred for ten (10) minutes at 80° C. (176° F.). Afterstirring time was completed, a separation that would be usable in theplant was seen in ten (10) minutes. Over a longer period more cleaningof the water layer was apparent. Tank 5067 is 25% by volume water. ABS&W run and the volumes seen in the separation were identical.

Lab Experiment #2:

The initial samples for Tank 5058 (Calumet Lubricants, Princeton, La.)presented for testing showed no significant BS&W. Apparently otheractivities that have been carried out on this tank had split out theupper layers. The tank was bomb sampled every three (3) feet from thetop of the fluid to the bottom of the tank. Samples from twenty-three(23) feet to the bottom of twenty-nine and a half (29′6″) feet showedboth a free water layer and a sludge layer below the water. Thesplitting efforts were applied to the material below the water layer.

Two hundred (200) ml of the twenty-six (26′) foot layer (sludge) wasmixed with one (1) ml of “505-SD-M” and heated to 65° C. (150° F.). Sixhundred (600) ml of water was mixed with five (5) ml of “A1000” andheated to 65° C. (150° F.). The two pots were combined and one hundred(100) ml of Calumet diesel was added. The mixture was stirred for ten(10) minutes using a magnetic stir bar and maintained between 140° F.and 150° F. After stirring was completed, commercially usable separationhad occurred in ten to fifteen (10-15) minutes. Longer separation timesyield a cleaner separation.

Lab Experiment #3:

The remainder of all of the samples from twenty-three (23′) feet to thebottom (Tank 5058) were mixed for a volume of twelve hundred (1200) ml.To this was added eighteen (1800) ml of water and fifteen (15) ml of“A1000.” With stirring the mixture was heated to 65° C. (140° F.). Whenthe mixture reached 65° C., six (6.0) ml of “505-SD-M” and one hundredand twenty (120) ml of Calument diesel were added. Stirring wascontinued at temperature for two (2) hours. When stirring was stopped,an oil/water separation in the four (4)-liter beaker occurred in lessthan ten (10) minutes. The sediment took longer to fall to the bottom.

Cost calculator:

(Gallons of sludge)×(0.005)×($30.00/gallon “505-SD-M”)

For Water: (Gallons of water)×(0.015)×($15.00/gallon “A1000”) For Diesel(Gallons of sludge)×(0.10)

Less than three volumes of water might be used, but the system appearsto be considerably less stable. If recycled water is used, the 0.015multiplier can be replaced with 0.009 for the “A-1000.” The ten (10%)percent diesel is very necessary. Diesel is recovered when the oil layeris later processed through the crude unit.

It is noted that the formulations, compositions, and applicationsdescribed herein generally and/or in detail were for exemplary purposesand are, of course, subject to many different variations. Because manyvarying and different embodiments may be made within the scope of theinventive concept(s) herein taught, and because many modifications maybe made in the embodiments herein detailed in accordance with thedescriptive requirements of the law, it is to be understood that thedetails herein are to be interpreted as illustrative and not in alimiting sense.

What is claimed is:
 1. A method of liquefying and dispersing crystallinewax in a petrochemical mixture, comprising the steps of: (a) chemicallytreating the crystalline wax in the petrochemical product to reduce thesurface tension of the crystalline wax, converting it to an amorphousform of wax, and treating the crystalline wax in the petrochemicalmixture with a surface active agent having a surface tension in water inthe range of about 10 to about 48 dynes per cm, reducing the crystallinewax's surface tension, including with the surface active agent in ahomogeneous mixture— about 15% to about 35% by weight butyl cellosolve;and about 5% to about 15% by weight of pine oil and a mixed catalystsolution made of saturated higher fatty acids, an alkyl phenol and anoil-water soluble copolymer of partially sulfonated, maleic anhydrideand polystyrene with a molecular weight ranging from about 2,000 toabout 2,000,000; and (b) dispersing the amorphous wax in a diluent. 2.The method of claim 1, wherein there is further included the step of:using a catalyst mixture in a range of about 0.5% to about 5% by weight.3. A method of liquefying and dispersing crystalline wax in apetrochemical mixture, comprising the steps of: (a) chemically treatingthe crystalline wax in the petrochemical product to reduce the surfacetension of the crystalline wax, converting it to an amorphous form ofwax, and treating the crystalline wax in the petrochemical mixture witha surface active agent having a surface tension in water in the range ofabout 10 to about 48 dynes per cm, reducing the crystalline wax'ssurface tension, wherein the surface active agent is a nonionicsurfactant, and wherein there is further included the step of: using, asa chemical composition mixture, a by-weight percent of the nonionicsurface active agent of about 48%, with about 32% butyl cellosolve andabout 17% pine oil acting as degreaser, about 2% of a mixture containingabout 70% higher fatty acids, about 29% a copolymer of maelic anhydrideand polystyrene and about 1% of catechol serving as a corrosioninhibitor; and (b) dispersing the amorphous wax in a diluent.
 4. Achemical mixture, comprising: wax, originally in crystalline form, butconverted to an amorphous form due to the presence of an additiveincluding a nonionic surface active agent, a hydrotrope-demulsifier, achelating agent and a wax plasticizer, wherein: said surface activeagent represents about 48% by weight; and there is further included:about 32% butyl cellosolve and about 17% pine oil, about 2% of a mixturecontaining about 70% higher fatty acids, about 29% a copolymer of maelicanhydride and polystyrene and about 1% catechol.
 5. A method ofliquefying and dispersing crystalline wax in a petrochemical mixture,comprising the steps of: (a-i) chemically treating the crystalline waxwith a surface active agent of a nonionic surfactant that is made up ofup to about 99.9% by weight of a nonionic surfactant and down to about0.1% by weight of a surface tension depressant, thereby converting thecrystalline wax to an amorphous form of wax, using a nonionicpolyethoxylate surfactant as the nonionic surfactant, wherein there isfurther included the step of: also adding with said nonionicpolyethoxylated compound in a homogeneous mixture— about 15% to about35% by weight butyl cellosolve, about 5% to about 15% by weight of pineoil and a mixed catalyst solution made of saturated higher fatty acids,an alkyl phenol and an oil-water soluble copolymer of partiallysulfonated, maleic anhydride and polystyrene with a molecular weightranging from about 2,000 to about 2,000,000; (a-ii) further,concurrently treating the dispersing crystalline wax in thepetrochemical mixture with a hydrotrope-demulsifier, a chelating agentand a wax plasticizer; and (b) dispersing the resultant amorphous wax ina diluent.